Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

ABSTRACT

A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,β fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application under 35 U.S.C. §121 ofU.S. patent application Ser. No. 12/985,439, filed on Jan. 6, 2011, andclaims the benefit under 35 U.S.C. §119(e) of U.S. ProvisionalApplication Ser. No. 61/360,026, filed on Jun. 30, 2010, the disclosuresof which are incorporated herein by reference in their entirety.

GOVERNMENT RIGHTS

This invention was made with United States Government support undergrant number W15P7T-08-C-P409 awarded by the United States Department ofDefense; grant number FA9550-10-1-0399 awarded by the Air Force Officeof Scientific Research; and grant number DE-SC000957 awarded by theUnited Stated Department of Energy. The government has certain rights inthe invention.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a joint universitycorporation research agreement: The Regents of the University ofMichigan, Princeton University, University of Southern California, andUniversal Display Corporation. The agreement(s) was in effect on andbefore the date the claimed invention was made, and the claimedinvention was made as a result of activities undertaken within the scopeof the agreement(s).

TECHNICAL FIELD

The present disclosure relates to organic films for use in organicelectronic devices.

BACKGROUND

Porphyrins are one of the most important biological molecules essentialfor life and responsible in nature for such oxidation-reductionreactions as photosynthesis in plants and respiration in animals.Synthetic porphyrins have broad applications as useful opto-electronicmaterials in different fields of organoelectronics, such as solar cells,photodetectors, and as catalysts in a variety of reactions. Advantagesof using porphyrins as opto-electronic materials include efficiency ofcharge separation and charge transport even in thick films of assembledporphyrins, strong absorbance in the visible region, high chemicalstability, and ability to tune optoelectronic properties. However, thereare some problems associated with application of porphyrins inorganoelectronics. Porphyrins have a modest spectral overlap with solarspectrum and the material preparation and isolation is difficult.Additionally, fluorescence of porphyrinoids in the near infrared (NIR)is quite rare. For a number of potential optoelectronic applicationsstrong absorption in NIR spectral region is desired. One of theapproaches to get absorption in NIR spectral region is by extending thesize of π-conjugation in the porphyrin system. The conjugation ofporphyrins can be extended through several modes of substitutioninvolving the (meso), (β,β), (β,meso) and (β,meso, β) positions. It hasbeen shown previously that some aromatic rings can be fused withporphyrins in (β,meso) and (β,meso, β) modes. These reactions requireactivation of porphyrin rings by metalation with nickel(II) oractivation of aromatic rings by multiple alkoxy-substitution. Nickel(II)porphyrins have rapid decay of the excited state due to nickel centered(d,d) quenching and at the same time demetalation of such porphyrinsdoes not have synthetic potential since it requires harsh conditions notsuitable with the presence of alkoxy groups (for example, concentratedsulfuric acid). Nickel(II) porphyrinoids have not found any applicationsin photovoltaics and no emission has been reported for such porphyrinscontaining nickel atom or donor alkoxy groups. Additionally, thisusually causes difficulties with synthesis, and isolation is possibleonly in small amounts. One of the most limiting factors in use inorganoelectronics of many derivatives of porphyrins with extendedconjugation is both their very low solubility and inability to sublime.

Almost all porphyrins, phthalocyanines and subphthalocyanines have ametal or heteroatom in the center. The ability of metals to coordinatewith different ligands may provide a new way to tune properties ofmacrocycles and, thus, enhance organoelectronic device performanceLiterature data shows that at least for some systems consisting ofmacrocycles such supramolecular organization through coordination bymetal centers can enhance conductivity and charge transport. Althoughcoordination chemistry of metalated macrocycles are very wellestablished, application of this strategy to change and improveoptoelectronic devices with use of such macrocycles as porphyrins,phthalocyanines, etc. still remains unrealized.

SUMMARY

According to an aspect of the present disclosure, a compound comprisinga non-activated porphyrin fused with one or more non-activatedpolycyclic aromatic rings or one or more non-activated hetrocyclic ringsis disclosed. In one embodiment, the compound comprises a non-activatedporphyrin fused with one or more non-activated polycyclic aromatic ringsand has a formula selected from the group consisting of:

wherein M is two hydrogen atoms or any element selected from the groupconsisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn,Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al,Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Th, and U; wherein R₁-R₃₇ are independently selectedfrom the group consisting of electron donors and acceptors, such ashydrogen, alkyl, fluoroalkyl, hydroxyl, alkoxy, halo (Cl, Br, I),chalcogens (S, Se, Te), mercapto group, amino, cyano, alkenyl, alkynyl,and aryl; and each dotted arc is all possible combinations of fusedrings, both aromatic and unsaturated or combination of both aromatic andunsaturated rings including four, five, six, seven, eight, ornine-membered rings, and all possible combination of fused heterocyclicrings with one or more heteroatoms, including all possible combinationsof all heteroatoms in all possible arrangement.

In another embodiment, the compound comprises a non-activated porphyrinfused with one or more non-activated heterocyclic rings and the compoundhas a formula selected from the group consisting of:

and

wherein M is two hydrogen atoms or any element selected from the groupconsisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn,Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al,Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Th, and U; wherein R₁-R₁₄ are independently selectedfrom the group consisting of electron donors and acceptors, such ashydrogen, alkyl, fluoroalkyl, hydroxyl, alkoxy, halo (Cl, Br, I),chalcogens (S, Se, Te), mercapto group, amino, cyano, alkenyl, alkynyl,and aryl. X is a heteroatom selected from the following list: O, S, Se,Te, N, P, As, Si, Ge, B; and each dotted arc is all possiblecombinations of fused rings, both aromatic and unsaturated orcombinations of both aromatic and unsaturated rings including four,five, six, seven, eight, or nine-membered rings, and all possiblecombinations of fused heterocyclic rings with one or more heteroatoms,including all possible combinations of all heteroatoms in all possiblearrangements.

According to an implementation of the present disclosure, a process forfusing one or more non-activated polycyclic rings to a non-activatedporphyrin core comprises heating a quantity of precursor porphyrins to afusion temperature in an inert gas environment; holding the precursorporphyrins at the fusion temperature for a predefined period of timeuntil the precursor porphyrins melt and form a mixture of fusedporphyrins; cooling the mixture of fused porphyrins to room temperature;and separating the mixture of fused porphyrins into various fusedporphyrin compounds. Presumably, the fusion takes places when theprophyrins are in the melted phase. Thus, generally, the fusiontemperature is above the melting point of the precursor porphyrins.

The fusion of the non-activated porphyrins and one or more non-activatedpolycyclic aromatic rings or non-activated heterocyclic rings isachieved by thermal fusion. These fused porphyrins are not available byusing other methods reported for similar fusion reactions in literature(FeCl₃, FeCl₃/AgOTf, Sc(OTf)₃/DDQ, DDQ, PhI(OTf)₂/BF₃OEt₂,(p-BrPh)₃NSbCl₆, K/Na, F₄TCNQ). Thermal fusion of one or more polycyclicrings to a porphyrin core in meso,β fashion is carried out to obtainhybrid structures containing distorted porphyrin ring with annulatedaromatic rings. This ring fusion causes a significant distortion of theporphyrin away from planarity. The non-planar structure leads tobroadening and red shifting of absorption bands and an enhancedsolubility in organic solvents. Such meso,β fused porphyrins represent anew family of dyes with strong absorption across the solar spectrum andemission in NIR region. Suitable substituted meso,β substitutedporphryins also have significant absorption in both the visible and NIRpart of the spectrum. These materials make excellent candidates foractive materials in solar cells and photodetectors, where strongabsorption in the visible and NIR are crucial. They also havesignificant benefits for application in NIR light emitting diodes.Fusion of polycyclic rings with a diprophyrin or porphyrin tape has beenpreviously disclosed in the art, but fusion of polycyclic rings withsingle porphyrin cores or fusion by thermal treatment without activatingagents have not been achieved previously. The preparation and use offusing polycyclic aromatic hydrocarbons and heterocycles to porphyrinsextend and broaden absorption, and help to modify the solubility,crystallinity, and film forming properties of pophyrins.

The method of the present disclosure enables fusion of porphyrin ringsto one or more polycyclic aromatic rings or heterocyclic rings withoutactivation of the porphyrin rings or activation of the aromatic rings orheterocyclic rings.

According to another aspect of the present disclosure an organicphotosensitive device incorporating the fused porphyrin materialdisclosed herein and a method for fabricating such organicphotosensitive device are also disclosed. Such organic photosensitivedevices include photovoltaic devices which convert light intophotocurrent and thereby supply electrical power to a circuit and otherembodiments such as photodetectors, for example.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the synthesis of mono (ZnMFBPP), doubly (ZnDFBPP) andquardruply (ZnQFTPP) fused pyrene-porphyrins.

FIG. 2 shows the absorption spectra of ZnBPP, ZnMFBPP, ZnDFBPP indichloromethane solution.

FIG. 3 shows the absorption spectra of ZnBPP, ZnMFBPP, ZnDFBPP in thethin film.

FIG. 4 shows room temperature emission spectra of ZnMFBPP, ZnDFBPP indichloromethane.

FIG. 5 shows the absorption spectra of ZnQFTPP in pyridine solution andin the thin film

FIG. 6 illustrates the synthesis of ZnBTP and ZnFBTP.

FIG. 7 shows the absorption spectra of ZnBTP and ZnFBTP indichloromethane solution and in the thin film.

FIG. 8 shows the JV characteristics for ZnDFBPP and ZnPh2DFBPP inITO/spin-cast porphyrin layer (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000Å) devices.

FIG. 8 a shows the JV characteristics for ZnDFBPP in ITO/ZnDFBPP (100Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices. Conventional referencedevice using 400 Å copper phthalocyanine (CuPc) as donor layer anddevice using spin-cast donor layer of ZnBPP with addition of4,4′-bipyridine also shown for reference.

FIG. 9 shows the EQE response for ZnDFBPP in ITO/spin-cast porphyrinlayer (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIG. 9 a shows the EQE response for ZnDFBPP in ITO/donor layer (100Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) device, a reference device using400 Å CuPc as the donor layer and another reference device usingspin-cast donor layer of ZnBPP with addition of 4,4′-bipyridine alsoshown for reference.

FIG. 10 shows the EQE response for in situ generated by thermalannealing at 530° C. ZnQFTPP in ITO/porphyrin (100 Å)/C₆₀ (400 Å)/BCP(100 Å)/Al (1000 Å) devices.

FIG. 11 shows the JV characteristics for ZnFBTP in ITO/porphyrin (100Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIG. 12 shows the EQE response for ZnFBTP in ITO/porphyrin (100 Å)/C₆₀(400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIG. 13 illustrates the synthesis of cyanophenyl porphyrin dimer

FIG. 14 illustrates the synthesis of pyrene porphyrin trimer.

FIG. 15 shows the UV/VIS spectra of ZnBTP, cyano-phenyl porphyrin dimerand pyrene porphyrin trimer in the thin film.

FIG. 16 shows the JV characteristics for cyano-phenyl porphyrin dimer inITO/porphyrin (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIG. 17 shows the JV characteristics for pyrene porphyrin trimer inITO/porphyrin (75 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIG. 18 shows the JV characteristics for bis-pyrene porphyrin inITO/porphyrin (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIG. 19 shows the JV characteristics for ZnBTP in ITO/porphyrin (100Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIG. 20 shows the JV characteristics for diphenyl porphyrin inITO/porphyrin (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices.

FIGS. 21( a)-21(p) show the various basic structures of porphyrins fusedwith polycyclic aromatic hydrocarbons according to an embodiment.

FIGS. 22( a)-22(u) show the basic structures of additional aromatichydrocarbons that can be fused with porphyrins: acenathphylene (a),phenanthrene (b, c), phenalene (d), coronene (j), acenes (k, l, m),rylenes (n, o, p, q), and pyrene (r).

FIGS. 23( a)-(g) show the basic structures of porphyrins fused withpolycyclic heterocyclic rings according to another embodiment.

FIGS. 24( a)-(l) show the basic structures of additional heterocyclicrings which can be fused with porphyrins: phenoxazine (a, X═O),phenothiazine (a, X═S), phenoselenazine (a, X═Se), phenotellurazine (a,X═Te), dihydrophenazine (a, X═NH, NR), benzo[b][1,4]oxazine (b, c, X═O),benzo[b][1,4]thiazine (b, c, X═S), benzo[b][1,4]selenazine (b, c, X═Se),benzo[b][1,4]tellurazine (b, c, X═Te), dihydroquinoxaline (b, c, X═NH,NR), benzofurane (d, i, j, X═O), benzothiophene (d, i, j, X═S),benzoselenophene (d, i, j, X═Se), benzotelluraphene (d, i, j, X═Te),indole (d, i, j, X═NH, NR, g, h), carbazole (f), dipyrrin (k, l, Y═BF₂,metal).

FIG. 25 shows the basic structure of porphyrin olygomers.

FIG. 26( a)-(f) shows ¹H NMR spectra of ZnBPP, ZnMFBPP, ZnDFBPP, ZnFBTP,cyano-phenyl porphyrin dimer and pyrene porphyrin trimer, respectively.

FIG. 27 is a schematic illustration of the architecture of an example ofa photosentive device incorporating the compounds disclosed herein.

FIG. 28 is a flowchart showing the method of fusing non-activatedporphyrins with one or more non-activated aromatic rings according tothe present disclosure.

Except where noted, all drawings are schematic and are not drawn toscale and are not intended to necessarily convey actual dimensions.

DETAILED DESCRIPTION I

According to an aspect of the present disclosure, mono-, doubly-,triply-, and tetra-fused porphyrins with aromatic rings in meso,β modeand a method of their preparation by thermal ring closure of the singlysubstituted porphyrins with appropriate polycyclic aromatic rings (e.g.naphthalene, pyrene, phenanthrene, etc) is described. The use of thesethermally fused porphyrins in donor/acceptor configuration devicestypical with common organic solar cells (i.e. copper phthalocyanine/C₆₀)is also described.

Thermal fusion of one or more polycyclic rings to a porphyrin core inmeso,β fashion to obtain hybrid structures containing a distortedporphyrin ring with annulated aromatic rings is schematically shownbelow for pyrene fused porphyrins.

One of the ways to overcome problems with solubility in extendedaromatic systems is to introduce out-of-plane distortion. Fusion in(meso,β mode with polycyclic aromatic rings (PAHs—rings, consist ofseveral condensed benzene rings, such as naphthalene or pyrene rings)should cause such distortion due to unfavorable interactions between βpyrrolic protons of porphyrin ring and protons at the α-position ofaromatic rings. In contrast, fusion in (β,meso, β) mode with anthracenerings leads to the formation of planar fused porphyrins with extremelylow solubility even by placing multiple solubilizing alkoxy groups. Inother (β,meso) fused systems, the distance between two mentionedhydrogen atoms may not lead to large distortion and, therefore, suchsystems as azulene-fused porphyrins display modest solubility. For thefusion of pyrene rings, all previous attempts to fuse unsubstitutedpyrene ring were unsuccessful and is possible only as fusion of onealkoxy-activated pyrene ring. The obtained pyrene-fused products werenot reported to have emission.

The present disclosure describes a new method of preparation of multiplyfused aromatic rings with a porphyrin core which does not require anyactivation and is possible without any solvents and reagents bypreviously unknown flash pyrolysis of porphyrins singly connected withthe corresponding aromatic ring at high temperatures. At elevatedtemperatures (500-530° C. under nitrogen), bis-pyrenyl substitutedporphyrin ZnBPP undergoes a thermal ring closure yielding the desiredmono-ZnMFBPP and regioisomeric doubly-fused porphyrins ZnDFBPP (FIG. 1).The product ratio (ZnMFBPP:ZnDFBPP) and reaction yield can be controlledby varying the reaction time. The inventors have found that thermalannealing thin films or small amounts (50-100 mg) ofbis-pyrenyl-porphyrin ZnBPP yields ZnDFBPP nearly quantitatively. Thisreaction has also proven to be scalable, in excess of several grams,although with smaller isolated yields of ZnDFBPP of about 25-35%.

The major byproduct in large scale reactions, comprising 35-40% of theporphyrinic product, involves the loss of one di-tert-butylphenyl groupfrom ZnDFBPP. While this byproduct affects yields of ZnDFBPP, the lossof a di-tert-butylphenyl groups does not affect the optical propertiesof the compound, such that the yield of NIR absorbing and emittingmaterial remains high. All meso-porphyrinic positions appear to beexhaustively fusible, such that fusion is achievable even fortetrakis-pyrenyl-porphyrin ZnTPP to form the quadruply fused productZnQFTPP therefore, the number of fusion sites of the substituents atmeso-porphyrinic positions does not have a limit.

Pyrene ring fusion is verified by the mass spectra of the obtainedproducts, that clearly indicate the loss of two (for ZnMFBPP;[M]⁺=1146.4581), four (for ZnDFBPP; [M]⁺=1144.4418) and eight protons(for ZnQFTPP; [M]⁺=1164.32) relative to the parent compounds ZnBPP([MH]⁺=1149.4834) and ZnTPP ([MH]⁺=1173.2915). Both regioisomers ofdoubly fused porphyrin anti-ZnDFBPP and syn-ZnDFBPP (1:1 ratio) wereobserved, and can be separated using column chromatography (anti-ZnDFBPPis shown in FIG. 1). Structure assignment for both regioisomers can bedone by NMR spectroscopy based on the number of equivalentdi-tert-butyl-phenyl groups, since regioiomer anti-ZnDFBPP has only oneset and syn-ZnDFBPP has two independent sets of signals of protons forthe di-tert-butylphenyl groups. Unlike regioisomeric fused porphyrintapes with strong shape dependence of their photophysical properties,anti-ZnDFBPP and syn-ZnDFBPP have quite similar properties.

Referring to the flowchart 200 in FIG. 28, the process for fusing one ormore non-activated polycyclic rings to a non-activated porphyrin coreaccording to an implementation of the present disclosure comprisesheating a quantity of precursor porphyrins to a fusion temperature in aninert gas environment (block 210) and holding the precursor porphyrinsat the fusion temperature for a predefined period of time until theprecursor porphyrins melt and form a mixture of fused porphyrins (block220). The mixture of fused porphyrins is then cooled to room temperature(block 230) and separated into various fused porphyrin compounds (block240). The fused porphyrin can be separated using column chromatographythen further purified by recrystallization.

An example of the thermal fusion process for thermally fusingnon-activated porphyrins with one or more non-activated polycyclicaromatic rings will now be described using the fusion process conductedby the inventors using bis-pyrenyl-porphyrin ZnBPP as the precursornon-activated porphyrin material. A quantity of bis-pyrenyl-porphyrinZnBPP*MeOH (1 g, 0.845 mmol) was placed into a glass tube (directly orin an appropriate container such as a glass boat). The glass tube wasplaced into a furnace preheated to a fusion temperature in an inert gasenvironment (nitrogen, neon, or argon, for example) and held at thefusion temperature for a predefined time period until the precursormaterial melt and form a mixture of fused porphyrins.

The fusion takes places when the prophyrins are in the melted phase.However, potentially, an appropriate porphyrin may be fused withoutmelting. Thus, generally, the fusion temperature will depend on themelting (or transition) point of the starting porphyrin material to befused. For porphyrins with lower melting point, the fusion temperaturecan be lower than 500° C. For porphyrins with higher melting point, thefusion temperature could be higher than 530° C. Preferably, the fusiontemperature is above the melting (or transition) point of the precursorporphyrins.

For the quantity of bis-pyrenyl-porphyrin ZnBPP*MeOH (1 g, 0.845 mmol),the fusion temperature was between 500° C.-530° C. The furnace waspreheated to a fusion temperature of 530° C. and held at thattemperature for about 5 minutes. First, the furnace temperature rose to530° C. in 1-2 minutes and after additional approx. 1-2 minutes, theprecursor non-activated porphyrin material melted. The precursormaterial turned into a brown color and bubbles appeared. After about 0.5minutes, the glass tube was removed from the furnace and the mixture offused porphyrins was cooled to room temperature while under the inertgas environment. Prolonged heating causes reduced yields of the doublyfused product ZnDFBPP.

In general, the optimal dwell time at the fusion temperature is theduration which results in the maximum amount of the desired fusedproduct in the reaction mixture. This dwell time can be foundexperimentally. The fusion dwell time will depend on the nature of thepolycyclic aromatic rings and stability of the products at hightemperature. If the fusion dwell time is short, a significant amount ofthe starting porphyrin material may be present in the reaction mixture.If the fusion dwell time is too long, already formed fused porphyrinscan decompose (for example, with the loss of one or two arylsubstituents such as di-tert-butyl-phenyl group).

The amount of desired fused products will increase until all startingmaterial is converted into fused products. After that, if competingreactions exist, such as decomposition, the amount of fused product willdecrease. Therefore, one can determine the fusion dwell time that wouldproduce the maximum amount of the fused product experimentally.

The inventors repeated the process five additional times with new 1 gbatches of the precursor non-activated porphyrin material resulting in atotal of about 6 g of the mixture of fused porphyrin ZnBPP. The scalableprocess however can be done in larger amounts of starting porphyrin,this would lead to the final fused products, however, with smalleryields.

The crude mixture of fused porphyrins was dissolved in dichloromethane(100 ml) with addition of hexanes (300 ml) and pyridine (5 ml) andseparated into various fused porphyrin compounds by graduated elution onan alumina column chromatograph (400 g). An elution of the mixture offused porphyrins with dichloromethane gave first fraction whichcontained compound ZnMFBPP. Next, an elution withhexanes:dichloromethane:pyridine=700:300:5 mixture gave crude doublyfused porphyrin ZnDFBPP which was purified by recrystallization fromdichloromethane by layered addition of methanol to give ZnDFBPP (about93-95% purity 1.80 g, 30%). An elution withdichloromethane:pyridine=1000:5 mixture gave doubly fused porphyrin withthe loss of one di-tert-butyl-phenyl group which was purified byrecrystallization from dichloromethane-pyridine by layered addition ofmethanol (2.3 g, 38%). Higher purity doubly fused porphyrin ZnDFBPP canbe obtained by column chromatography on silica gel (gradient elutionwith hexanes:dichloromethane mixtures 1000:50 to 800:200). The firstfraction containing compound ZnMFBPP was additionally purified by silicagel column (gradient elution with hexanes:ethyl acetate mixtures 1000:5to 1000:15) and crystallized from dichloromethane by layered addition ofmethanol to give compound ZnMFBPP (0.54 g, 9%).

According to another aspect of the present disclosure, the process forfusing non-activated porphyrins can be incorporated into a process forfabricating a photosensitive device such that the non-activatedporphyrins in the donor material can be fused in the device form factor.When carried out in the device form factor, the thermal fusion isconducted with the precursor porphyrins in thin films by spin-coatingthe precursor porphyrins from appropriate solution on glass, indium tinoxide or other surfaces.

One such method for fabricating a photosensitive device forms a planardonor-acceptor heterojunction device. The method comprises depositing afirst electrode layer on a suitable substrate and depositing a layer oforganic donor material over the first electrode, thus forming an interimstructure, wherein the organic donor material comprises a precursorporphyrin material. The interim structure is then heated to a fusiontemperature for the particular precursor porphyrin material. The heatingis conducted in an inert gas environment (e.g. nitrogen or other inertgas) and held at the fusion temperature for a predefined period of timeuntil the precursor porphyrin material melts and forms a layer ofmixture of fused porphyrins. A layer of an organic acceptor material isthen deposited over the layer of the organic donor material, wherein theorganic acceptor material layer is in direct contact with the organicdonor material layer, whereby the organic donor material layer and theorganic acceptor material layer form a photoactive region. A secondelectrode layer is then deposited over the organic acceptor materiallayer. The first electrode and the second electrodes can be anode andcathode, respectively and the suitable electrode materials are wellknown to the art. For example, the anode can be formed using atransparent electrode material such as ITO (indium tin oxide) and thecathode can be formed using a metal such as silver. The device mayfurther comprise a layer of bathocuproine (BCP) disposed between theacceptor material layer and the second electrode, the BCP functioning asan exciton blocking layer in the device.

According to another aspect, a method for fabricating a photosensitivedevice having a bulk donor-acceptor heterojunction is disclosed. Themethod comprises depositing a first electrode layer on a suitablesubstrate and depositing a layer of a mixture of an organic donormaterial and an organic acceptor material over the first electrode, thusforming an interim structure, wherein the organic donor materialcomprises a precursor porphyrin material. The interim structure is thenheated to a fusion temperature for the particular precursor porphyrinmaterial for fusing the porphyrins. The heating is conducted in an inertgas environment and held at the fusion temperature for a predefinedperiod of time until the precursor porphyrin material in the mixture ofthe organic donor and acceptor materials melts and forms fusedporphyrins. The fused porphyrins and the organic acceptor material forma photoactive region having a bulk heterojunction. Subsequently, otherlayers of the photosensitive device, such as a second electrode layer,is deposited over the photoactive region. The device may furthercomprise a layer of BCP disposed between the photoactive region and thesecond electrode, the BCP functioning as an exciton blocking layer inthe device.

According to another aspect, a quantity of fused porphyrin compounds canbe used to form a donor layer of a photoactive region in aphotosensitive device. The examples of PV devices whose JVcharacteristics are plotted in FIGS. 8-12, discussed below, werefabricated in such manner.

As described above, the donor materials of the present disclosure can beused to form a bulk heterojunction configuration of a photosensitivedevice. Using solution processing, more than one component can be mixedor blended for deposition including donor and acceptor materialstogether. The donor materials can be mixed with a soluble acceptor, suchas PCBM or PTCDI, to spin-coat or spin-cast the photoactive regionhaving a bulk heterojunction configuration. The fused non-activatedporphyrin donor materials disclosed herein can be co-deposited withother materials, such as another donor material or an acceptor material.

There are several major differences between the porphyrins fused in(meso,β) mode with aromatic rings as disclosed in the present disclosurecompared to previously reported fused porphyrins in (meso,β) and(β,meso,β) modes. (1) First, the fusion of one or two pyrene rings in(meso,β) mode with a porphyrin molecule leads to a product withsubstantially higher solubility. In contrast, even the presence ofseveral alkoxy groups in porphyrins fused with anthracene rings in(β,meso, β) mode gives compounds with very limited solubility. Thus,distortion in (meso,β) mode is an important structural factor for thecontrol of different properties of porphyrinoids. (2) Next, using thethermal fusion method disclosed herein, a direct fusion is possiblewithout any activation of porphyrins (e.g. porphyrin rings withnickel(II) metalation and PAHs with alkoxy groups) for unsubstitutedPAHs rings with different metalated porphyrins (Zn, Pt, Pd, Cu, Pb,etc). Moreover, fusion of unactivated aromatic rings with unactivatedporphyrin rings cannot be achieved by known methods for similar fusions.

The thermal fusion process does not require any solvents and reagents.Thus, because of its efficiency, the thermal fusion can be described as“click” chemistry reaction, which can be used for generating differentfused products in situ by annealing thin films of starting non-fusedporphyrins directly on electrodes (e.g., ITO) during manufacture ofoptoelectronic devices. (3) The fused non-activated porphyrins of thepresent disclosure exhibit emission in NIR spectral region with one ofthe highest efficiencies reported in literature with quantum yields ofemission gradually increasing with the number of fused sites in goinginto NIR from 3.3% for the starting non-fused porphyrin ZnBPP at 590 and640 nm to 8% for the mono-fused porphyrin ZnMFBPP at 716 nm and 10% forthe doubly fused porphyrin ZnDFBPP at 816 nm. This trend is quitedifferent from the effect of extending conjugation in other porphyrins.Thus, porphyrinoids in general are very poor emitters in NIR spectralregion and NIR emission beyond 720 nm from other fused systems involvingmeso position have not been reported.

FIG. 1 shows the synthesis of mono (ZnMFBPP), doubly (ZnDFBPP) andquardruply (ZnQFTPP) fused pyrene-porphyrins. FIG. 2 shows theabsorption spectra of ZnBPP, ZnMFBPP, ZnDFBPP in dichloromethanesolution. FIG. 3 shows the absorption spectra of ZnBPP, ZnMFBPP, ZnDFBPPin the thin film. FIG. 4 shows the room temperature emission spectra ofZnMFBPP, ZnDFBPP in dichloromethane. FIG. 5 shows the absorption spectraof ZnQFTPP in pyridine solution and in the thin film.

Fusion with heterocyclic rings is also potentially interesting reactionto get heterocyclic-fused porphyrins. No reactions of direct fusion ofheterocyclic rings with porphyrins have been reported so far. Thiophenesand thiophene-containing compounds represent one of the most usefulheterocyclic system for organoelectronics and the inventors were able toachieve direct fusion of 3-substituted thiophene ring to porphyrins in(meso,β) mode with the formation of fused thiophene-porphyrin hybrid,which can be done both by thermal flash pyrolysis and by iron(III)chloride mediated ring closure.

FIG. 6 shows synthesis of ZnBTP and ZnFBTP. FIG. 7 shows the absorptionspectra of ZnBTP and ZnFBTP in dichloromethane solution and in the thinfilm.

The fused non-activated porphyrins have absorption shifted to deep redand NIR spectral regions and are promising materials to get highefficiency solar cells and for other applications, where NIR spectralregion is critically important for device performance. These materialscan provide better exciton diffusion length and better charge transport.FIGS. 8-12 show various measured performance characteristics of someexamples of photovoltaic devices fabricated with fused porphyrins as theorganic donor material. FIG. 8 shows the JV characteristics for ZnDFBPPand ZNPh2DFBPP in ITO/spin-cast porphyrin layer (100 Å)/C₆₀ (400 Å)/BCP(100 Å)/Al (1000 Å) devices as measured by the inventors. FIG. 8 a showsthe JV characteristics for ZnDFBPP in ITO/ZnDFBPP (100 Å)/C₆₀ (400Å)/BCP (100 Å)/Al (1000 Å) devices as measured by the inventors. The JVcharacteristics of conventional devices, one using 400 Å copperphthalocyanine (CuPc) as the donor layer and another using the spin-castdonor layer of ZnBPP (see FIG. 1) with addition of 4,4′-bipyridine arealso shown in FIG. 8 a for reference.

The π-systems of the fused pyrene moieties in ZnDFBPP are not stericallyhindered and are, therefore, suitable for intermolecular attractivepyrene-pyrene interactions. This leads to significant red-shiftedabsorption in the thin films (up to 90 nm in some cases, for example byspin-casting from toluene). Conversely, porphyrin ZnDFBPP has two bulkydi-tert-butyl phenyl groups at the meso positions of the porphyrin ring,limiting direct overlap with the π-system of the porphyrin chromophore.Control of such intermolecular interactions has been implicated as animportant factor in kinetically suppressing losses to open circuitvoltage (V_(oc)), which is thermodynamically limited by the interfacialenergy level offset (ΔE_(DA)) between HOMO_(donor)-LUMO_(acceptor).where HOMO is highest occupied molecular orbital and LUMO is lowestunoccupied molecular orbital. FIG. 8 illustrates the performance ofsolar cells (the current density vs. voltage (J-V) characteristics)incorporating fused pyrene porphyrin ZnDFBPP as a donor by usingspin-casting technique. FIG. 8 a illustrates the performance of solarcells (the current density vs. voltage (J-V) characteristics)incorporating fused pyrene porphyrin ZnDFBPP as a donor and referencecopper phthalocyanine (CuPc) cell by thermal evaporation, and referenceZnBPP/4,4′-bipyridyl cell by using spin-casting technique. The cellstructure is ITO/ZnDFBPP (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å),similar to that used for the copper phthalocyanine (CuPc) reference celland related porphyrin donor based cells. The current density vs. voltage(J-V) characteristics were measured in the dark and under simulated 1sun (1 kW/m²) AM1.5G illumination. Efficiencies were determined aftercorrection for spectral mismatch between Xe source lamp and ASTM G173-03global. Overall, thin layers (100 Å) of thermally evaporated porphyrinZnDFBPP yield a power conversion efficiency (PCE)>1%, which is close tothat of the reference (CuPc, 400 Å/C₆₀) device. The open circuit voltageof porphyrin ZnDFBPP and CuPc are comparable, even though ΔE_(DA) forCuPc/C₆₀ couple is larger (1.7 eV) than that for porphyrin ZnDFBPP/C₆₀(1.1 eV). This underscores the importance of attending to molecularstructure when considering materials to suppress losses in V_(oc). Theshort circuit current-density of J_(sc)=5.69 mA/cm² obtained for theporphyrin ZnDFBPP device is among the highest values reported forporphyrin solar cells and 32% higher than for standard CuPc cell. Thisenhancement appears to be due to panchromatic response up to 950 nm,with peak values of >7% in the 850-900 nm region (FIG. 9 a). Therelatively high EQE demonstrates the utility of employing intensebroadband absorption throughout the visible and NIR for achievingenhanced solar energy conversion efficiency.

FIG. 9 illustrates the performance of solar cells (EQE response)incorporating fused pyrene porphyrin ZnDFBPP as a donor by usingspin-casting technique. FIG. 9 a illustrates the performance of solarcells (EQE response) incorporating fused pyrene porphyrin ZnDFBPP as adonor and reference copper phthalocyanine (CuPc) cell by thermalevaporation, and reference ZnBPP/4,4′-bipyridyl cell by usingspin-casting technique. The cell structure is ITO/ZnDFBPP (100 Å)/C₆₀(400 Å)/BCP (100 Å)/Al (1000 Å), similar to that used for the copperphthalocyanine (CuPc) reference cell and related porphyrin donor basedcells. FIG. 9 a shows one of the best NIR EQE response for organic dyesof 7.5% at peak max=860 nm.

FIG. 10 shows the EQE response for ZnQFTPP in ITO/porphyrin (100 Å)/C₆₀(400 Å)/BCP (100 Å)/Al (1000 Å) devices generated in situ by thermalannealing at 530° C. Thermal annealing of starting porphyrins can bedone in situ on ITO or other transparent electrode just by spin-castingof non-fused porphyrins (e.g. ZnBPP, ZnTPP) and annealing at 530° C.under nitrogen for 5 minutes, these films can be used for devicefabrication directly without further processing the donor layer. FIG. 11shows the JV characteristics for ZnFBTP in ITO/ZnFBTP (100 Å)/C₆₀ (400Å)/BCP (100 Å)/Al (1000 Å) devices as measured by the inventors. FIG. 12shows the EQE response for ZnFBTP in ITO/porphyrin (100 Å)/C₆₀ (400Å)/BCP (100 Å)/Al (1000 Å) devices as measured by the inventors. Thisdata shows that porphyrins fused with heterocyclic rings can also beused as donor layers for organic solar cells. FIG. 12 illustrates theperformance of solar cells (EQE response) incorporatingbenzothienyl-fused porphyrin ZnFBTP as a donor by thermal evaporationwith photovoltaic response from porphyrin extended up to 1100 nm.

Olygoporphyrins singly connected at meso position were never applied tophotovoltaic (PV) devices before. Such porphyrin olygomers can be usedin PV devices with or without coordinative additives. Such porphyrinolygomers are shown in FIGS. 13-17 and 25. FIG. 13 shows the synthesisof a porphyrin dimer, specifically a cyano-phenyl porphyrin dimer. FIG.14 shows synthesis of pyrene porphyrin trimer. FIG. 15 shows UV/VISspectra of ZnBTP, cyano-phenyl porphyrin dimer and porphyrin trimer inthe thin film as measured by the inventors. FIG. 16 shows the JVcharacteristics for cyano-phenyl porphyrin dimer in ITO/porphyrin (100Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices as measured by theinventors. FIG. 17 shows the JV characteristics for pyrene porphyrintrimer in ITO/porphyrin (75 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å)devices as measured by the inventors. Photophysical properties ofolygoporphyrins are different from monoporphyrins. Some examples are:faster hole hopping from one porphyrin unit to another; and porphyrinunits are electronically coupled much stronger than two separateporphyrin units. This causes broadening of absorption spectrum withbetter overlap with solar spectrum (see FIG. 15). Besides thatelectronic coupling between porphyrin units should potentially providebetter charge transport which is essential for getting materials withlarger exciton diffusion length. Some problems involving applications ofolygoporphyrins include film morphology (formation of aggregates), poorsolubility, etc. The data in FIGS. 16 and 17 shows that olygoporphyrins(dimer, trimer) give photoresponse as donor layers by using spin-castingtechnique meaning that there is no problems with morphology of thinfilms, charge separation and charge transport. Therefore, this opensopportunities for their applications in devices with variousarchitecture where olygoporphyrins serve as donor materials. Advantagesof olygoporphyrins can be better organization of the thin films togetherwith better overlap with solar spectrum as illustrated by FIG. 15.

According to another aspect of the present disclosure, the use ofcoordinative additives to porphyrins, pthalocyanines, subphthalocyaninesin a donor/acceptor configuration typical with common organic solarcells (i.e. copper phthalocyanine/C₆₀) will now be described. In ourinitial implementation, we used porphyrins, porphyrin oligomers,phthalocyanines and subphthalocyanines with coordinative additives, suchas pyridines, as donors and paired them with the acceptor C₆₀.

By coordination of the above mentioned macrocycles with coordinativeadditives containing, for example, basic nitrogen atom gives possibilityto change and tune the energy levels of macrocycles as well as changethe morphology of the thin films. From the data obtained by theinventors and shown in FIGS. 16-20, it is clear that addition of suchrepresentative coordinative compounds as pyridine and 4,4′-bipyridyl,containing one basic nitrogen atom (pyridine) or two basic nitrogenatoms (4,4′-bipyridyl) significantly improves performance of thephotovoltaic cells.

First, the addition of coordination additives prevents aggregationgiving much better open circuit voltages especially for compounds withpronounced tendency for aggregation—from 0.3 V to 0.44 V for diphenylporphyrin (FIG. 20), from 0.35 V to 0.56 V for porphyrin dimer (FIG.16). Secondly, the addition of coordination additives improves Jsc andfill factor as well. This can be illustrated, for example, by increasingJsc from 2.17 to 2.87 mA/cm² and fill factor from 0.42 to 0.51 forbenzothiophene substituted porphyrin (FIG. 19). Examples: FIG. 16 showsthe JV characteristics for porphyrin dimer as one of the representativemembers of olygoporphyrins in ITO/porphyrin (100 Å)/C₆₀ (400 Å)/BCP (100Å)/Al (1000 Å) devices by using spin-casting method to deposit aporphyrin layer. This demonstrates the utility of olygoporphyrins asdonor layers in organic photovoltaic cells. Device performance issignificantly improved by using coordination additives, such as4,4′-bipyridyl, which prevents aggregation and increases open circuitvoltage, short circuit current and fill factor. The overall deviceperformance can be improved by more than 2 times.

FIG. 18 shows the JV characteristics for bis-pyrene porphyrin ZnBPP inITO/porphyrin (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices byusing spin-casting method to deposit the porphyrin layer. Deviceperformance is improved by almost 2 times by using pyridine as acoordination additive and further improved by about 20% by using4,4′-bipyridyl as a coordination additive. The use of coordinationadditives increases open circuit voltage, short circuit current and fillfactor, and, thus, overall performance by about 2.25 times. FIG. 19shows the JV characteristics for bis-(3-benzothienyl)-porphyrin inITO/porphyrin (100 Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices byusing spin-casting method to deposit the porphyrin layer. Deviceperformance is improved by about 2 times by using pyridine as acoordination additive and further by using 4,4′-bipyridyl as acoordination additive. The use of coordination additives increases opencircuit voltage, short circuit current and fill factor. FIG. 20 showsthe JV characteristics for diphenyl porphyrin in ITO/porphyrin (100Å)/C₆₀ (400 Å)/BCP (100 Å)/Al (1000 Å) devices by using spin-castingmethod to deposit the porphyrin layer. Device performance is improved byusing pyridine and further by about 2.5 times using 4,4′-bipyridyl as acoordination additive. This result and the results above suggest thatsuch great improvement in device performance by using additives and spincasting method to deposit donor layer has general applications.

All of the fused porphyrin compounds listed above and those depicted inFIGS. 21-24 are a new class of absorption material for application inorganoelectronics. The basic structure of the new material can be seenin FIGS. 21( a)-(p) and FIGS. 23( a)-(g). FIGS. 21( a)-(p) show thebasis structures of porphyrins fused with polycyclic aromatichydrocarbons. FIGS. 23( a)-(g) show the basic structures of pophyrinsfused with polycyclic heterocyclic rings. In the compositions shown inFIGS. 21 and 23, M is two hydrogen atoms representing free baseporphyrins or any element selected from the following group: Mg, Ca, Sr,Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co,Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn,Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th,and U. Each of the R₁-R₅₄ are independently selected from the groupconsisting of electron donors and acceptors, such as hydrogen, alkyl,fluoroalkyl, hydroxyl, alkoxy, halo (Cl, Br, I), chalcogens (S, Se, Te),mercapto group, amino, cyano, alkenyl, alkynyl, and aryl. The termshalo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, heterocyclic grouparyl, aromatic group, and heteroaryl are known to the art and aredefined, for example, in U.S. Pat. No. 7,279,704 at cols. 31-32, thedisclosure of which is incorporated herein by reference. In FIGS. 23(a)-(g), X is a heteroatom from the following list: O, S, Se, Te, N, P,As, Si, Ge, B. X can have two bonds as depicted or X can havecoordination with additional one, two or three bonds with one, two orthree ligands.

The dotted arcs in the FIGS. 21 and 23 can be all possible combinationof fused rings (both aromatic and unsaturated or combination of botharomatic and unsaturated rings including four, five, six, seven, eight,or nine-membered rings) and all possible combination of fusedheterocyclic rings with one or more heteroatoms, including all possiblecombinations of all heteroatoms in all possible arrangement. Each of thedotted arc can be the same ring, or different rings (difference by sizeof rings and composition of rings).

Two fused ends of porphyrins can be the same or different. Two fusedends of porphyrins can be naphthalene, anthracene, pyrene and thiophenerings as mentioned above or other polycyclic aromatic rings shown inFIGS. 22 and 24. Specifically, FIGS. 24( a)-(l) show heterocyclic rings.In FIGS. 22 and 24, the fusion position on the polycyclic aromatic ringsare marked with a wave-line and the connection with meso position of theporphyrins is marked with a black dot. In FIGS. 22( a)-(u), i, j, and mare each independently 0-100. FIGS. 22( a)-22(u) show the basicstructures of additional aromatic hydrocarbons that can be fused withporphyrins: acenathphylene (a), phenanthrene (b, c), phenalene (d),coronene (j), acenes (k, l, m), rylenes (n, o, p, q), pyrene (r).

According to an aspect of the present disclosure the fused non-activatedporphyrins and olygoporphyrins described herein can be incorporated in adonor/acceptor configuration as an optoelectronic material. For examplethe fused non-activated porphyrins and olygoporphyrins can be pairedwith acceptor materials to form the donor/acceptor heterojunctions ofthe photoactive regions in photosensitive devices. Examples of thesuitable acceptor materials are C₆₀, C₇₀, C₈₄, F₁₆—CuPc, PTCBI, PTCDA,PCBM and PTCDI to name a few.

The donor/acceptor heterojunctions of the photoactive regions utilizingthe donor materials of the present disclosure can be formed using any ofthe known suitable methods. For organic layers, such as the acceptormaterials and the donor materials of the present disclosure, preferredmethods include vacuum thermal evaporation, ink-jet deposition, such asdescribed in U.S. Pat. Nos. 6,103,982 and 6,087,196, the disclosures ofwhich are incorporated herein by reference in their entireties, organicvapor jet printing (OVJP), such as described in U.S. patent applicationpublication No. 2008/0233287, the disclosure of which is incorporatedherein by reference in its entirety. Other suitable deposition methodsinclude solution processing such as spin coating, spray coating, ordoctor blading. Solution processes are preferably carried out innitrogen or other suitable inert atmosphere.

The electrodes such as LiF/Al or BCP/Ag can be deposited by methodsknown in the art such as vacuum thermal evaporation.

FIG. 27 shows the architecture of an example of a photosensitive device100 comprising an first electrode 110, a second electrode 130 and aphotoactive region 120 disposed between the two electrodes. The firstelectrode 110 can be an anode typically formed of ITO, the secondelectrode 130 can be a cathode typically formed from Ag. The photoactiveregion 120 comprises the donor material based fused non-activatedporphyrins as disclosed herein and an acceptor material.

EXAMPLES

These and other aspects of the present disclosure will be furtherappreciated upon consideration of the following examples ofnon-activated porphyrins fused with non-activated polycyclic aromaticrings or heterocyclic rings. These examples are intended to illustratecertain particular embodiments of the invention but are not intended tolimit its scope, as defined by the claims.

Example 1 ZnMFBPP and ZnDFBPP

4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane. To a approx. 0.1M solution of 1-bromopyrene in toluene 10 mol % of Cl₂Pd(PPh₃)₂, 5equivalents of picolineborane and 10 equivalents of triethylamine wasadded. The reaction mixture was degassed with nitrogen and refluxedovernight. The reaction mixture was then quenched with water, toluenewas distilled off and the residue was subjected to column chromatographyon silica gel (gradient elution with hexanes-ethyl acetate mixtures from1:0 to 1000:5) to give 70-80% of4,4,5,5-tetramethyl-2-(pyren-1-yl)-1,3,2-dioxaborolane.

¹H-NMR (CDCl₃, 400 MHz): 1.51 (s, 12H), 8.02 (t, 1H, J=7.7 Hz),8.07-8.24 (m, 6H), 8.56 (d, 1H, J=9.7 Hz), 9.09 (d, 1H, J=9.7 Hz).

MALDI TOF mass spectrometry: 328 (M⁺), requires 328.16 for C₂₂H₂₁BO₂.

[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis-(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc (II) (See FIG. 1, ZnBPP). (A). NBS (5 g, 28 mmol,2.1 equiv.) was added to a stirred solution of[5,15-Bis(3,5-di-tert-butylphenyl)porphyrinato(2+κN²¹, κN²², κN²³,κN²⁴)zinc(II) (10 g, 13.33 mmol) in dichloromethane (700 ml) andpyridine (20 ml) at −10° C. (NaCl/ice bath) under nitrogen atmosphere.The reaction mixture was stirred at the same temperature for 10 minutes,then was allowed to warm to 0° C. in a water bath for 5 minutes and wasquenched with acetone (20 ml). The crude reaction mixture was passedthrough silica gel column, eluting with dichloromethane-pyridine mixture(100:1). All green-purple fractions were collected, solvents wereevaporated, the residue was dissolved in dichloromethane-pyridinemixture (95:5, 100 ml) and 200 ml of methanol was added to precipitatebromoporphyrin. All crystals were collected by filtration after 30minutes to give[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis-bromo-porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (7.5 g, 8.26 mmol, 62%).

(B). A mixture of the above dibromoporphyrin (6.33 g, approx. 6.97mmol), cesium carbonate (23.5 g, 70 mmol, 10 equiv.), Pd(PPh₃)₄ (800 mg,10 mol %) and 1-pyrenyl-tetramethyldioxaborolane (5.26 g, 16.03 mmol,2.3 equiv.) in toluene (800 ml) and pyridine (10 ml) was degassed andrefluxed in nitrogen atmosphere for 12 hours. The reaction mixture wascooled and passed consecutively through a pad of celite, silica gel andneutral alumina washing with toluene. Toluene was then distilled off invacuum and the residue was separated by crystallization fromdichloromethane-methanol to afford[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-Bis(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³, κN²⁴)zinc(II) (See FIG. 1, ZnBPP, 6 g, 5.2 mmol, 75%).

¹H-NMR (CDCl₃, 400 MHz): 1.47, 1.477 and 1.481 (s, 36H, atropoisomers),7.50 (dd, 2H, J=9.3, 10.6 Hz), 7.71-7.74 (m, 4H, atropoisomers),8.04-8.14 (m, 8H), 8.33 (t, 4H, J=7.2 Hz), 8.42 (d, 2H, J=9.1 Hz), 8.54(d, 2H, J=7.7 Hz), 8.63 (dd, 4H, J=0.8, 4.7 Hz), 8.86 (dd, 2H, J=2.8,7.7 Hz), 8.92 (d, 4H, J=4.7 Hz).

¹³C-NMR (CDCl₃, 75 MHz): 31.7, 35.0, 118.9, 120.8, 122.7, 122.8, 124.1,124.7, 125.2, 125.5, 126.2, 127.4, 127.5, 127.7, 127.9, 129.6, 129.8,129.9, 130.8, 131.3, 131.8, 132.0, 132.5, 132.6, 132.64, 133.4, 133.5,137.9, 141.6, 148.6, 150.7, 151.0. UV/VIS (CH₂Cl₂), λ, nm, (ε): 235(84899), 243 (120670), 264 (48136), 275 (69032), 308 (34871), 323(47186), 337 (54350), 427 (432531), 517 (6415), 551 (24905), 590 (5614).

HRMS: 1149.4834 (M⁺ and MH⁺), calcd. 1149.4808 for C₈₀H₆₉N₄Zn. MALDITOF: 1150 (M⁺ and MH⁺), requires 1149.48 for C₈₀H₆₉N₄Zn. Elementalanalysis for C₈₀H₆₈N₄Zn*MeOH: calcd: C, 82.25; H, 6.14; N, 4.74. found:C, 82.45; H, 6.25; N, 4.65.

[10,20-Bis(3,5-di-tert-butylphenyl)-4,5-(1,10-pyrenyl)-15-(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (See FIG. 1, ZnMFBPP) and[10,20-Bis(3,5-di-tert-butylphenyl)-4,5,14,15-bis-(1,10-pyrenyl)-porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (See FIG. 1, ZnDFBPP). The abovebis-pyrenyl-porphyrin ZnBPP*MeOH (550 mg, 0.465 mmol) in a glass tubeunder nitrogen flow was placed into an oven preheated to 530° C. Theoven temperature rose to 530° C. in 1-2 minutes and after additionalapprox. 1 minute, starting material melted. Heating continued for 20-30sec. until the reaction mixture turned into brown color and the firstbubbles appeared. The glass tube was cooled to room temperature undernitrogen. Prolonged heating causes reduced yield of the final productZnDFBPP and mono-fused product completely converted to ZnDFBPP. Thecrude mixture was dissolved in dichloromethane (500 ml) with addition ofpyridine (5 ml) and passed through a filter filled with silica gelwashing with dichloromethane. All purple fractions were collected,solvents evaporated. The residue was redissolved in dichloromethane andpassed through a filter filled with alumina, eluting withdichloromethane to get crude mono-fused product (ZnMFBPP) and withhexanes-dichloromethane-pyridine 700-300-5 mixture to get crudedoubly-fused product (ZnDFBPP). The products were subsequentlyrecrystallized from dichloromethane by layered addition of methanol.Yields: ZnMFBPP (50 mg, 9%), ZnDFBPP (190 mg, 36%).[10,20-Bis(3,5-di-tert-butylphenyl)-4,5-(1,10-pyrenyl)-15-(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (See FIG. 1, ZnMFBPP).

¹H-NMR (5%-pyridine-d5 in C₆D₆, 500 MHz): 1.49, 1.507, 1510 and 1.52 (s,36H, atropoisomers), 7.39 (d, 1H, J=9.5 Hz), 7.59 (d, 1H, J=9.5 Hz),7.78-7.85 (m, 3H), 7.94-7.96 (m, 2H), 8.01 (s, 1H), 8.02-8.09 (m, 5H),8.14 (d, 1H, J=9.5 Hz), 8.24 (d, 1H, J=8 Hz), 8.32 (d, 1H, J=8 Hz), 8.39(t, 1H, J=1.5 Hz), 8.45 (t, 1H, J=1.5 Hz), 8.53 (t, 1H, J=1.5 Hz), 8.55(d, 1H, J=4.5 Hz), 8.56 (t, 1H, J=1.5 Hz), 8.63 (d, 1H, J=4.5 Hz), 8.84(d, 1J, J=8 Hz), 9.03 (d, 1H, J=4.5 Hz), 9.09 (d, 1H, J=4.5 Hz), 9.13(s, 1H), 9.22 (d, 1H, J=4.5 Hz), 9.48 (d, 1H, J=8.5 Hz), 9.53 (d, 1H,J=4.5 Hz), 9.98 (s, 1H).

¹³C-NMR (5%-pyridine-d5 in C₆D₆, 500 MHz, 93.7 MHz): 30.2, 31.85, 31.86,31.89, 35.18, 35.20, 114.3, 119.0, 121.00, 121.03, 124.3, 124.6, 124.8,124.9, 125.0, 125.3, 125.4, 125.7, 125.8, 126.3, 126.4, 126.8, 127.4,127.7, 129.1, 130.7, 130.86, 130.90, 131.0, 131.2, 131.4, 131.6, 131.8,131.9, 132.2, 132.3, 132.5, 132.69, 132.75, 132.8, 132.9, 133.0, 133.8,133.9, 137.4, 138.0, 139.0, 143.4, 143.5, 146.8, 149.08, 149.10, 149.23,149.26, 150.3, 150.5, 150.6, 151.0, 151.8, 152.0, 152.3.

UV/VIS (CH₂Cl₂), λ, nm, (ε): 706 (43480), 495 (206480), 386 (40296), 339(45680), 324 (38374), 275 (51790), 264 (44275).

Emission: λ_(max), 722 nm; quantum yield, 8%. HRMS: 1146.4581 (M⁺),calcd. 1146.4573 for C₈₀H₆₆N₄Zn. Elemental analysis for C₈₀H₆₆N₄Zn*MeOH:calcd.: C, 82.39; H, 5.97; N, 4.74. found: C, 82.69; H, 5.91; N, 4.86.

[10,20-Bis(3,5-di-tert-butylphenyl)-4,5,14,15-bis-(1,10-pyrenyl)-porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (See FIG. 1, ZnDFBPP).

¹H-NMR (5%-pyridine-d₅ in C₆D₆, 25° C., 500 MHz, two regioisomers):1.53, 1.59 and 1.61 (s, 36H, regioisomers), 7.81 and 7.82 (d, 2H, J=8Hz, regioisomers), 7.91-8.03 (m, 8H), 8.1 and 8.17 (t, 2H, J=1.5 Hz,regioisomers), 8.26 and 8.28 (d, 2H, J=8.5 Hz, regioisomers), 8.40, 8.55and 8.62 (d, 4H, J=1.5 Hz, regioisomers), 9.00 and 9.08 (d, 2H, J=4.5Hz, regioisomers), 9.07 and 9.12 (s, 2H, regioisomers), 9.28 and 9.36(d, 2H, J=4.5 Hz, regioisomers), 9.33 and 9.35 (d, 2H, J=8 Hz,regioisomers), 9.78 and 9.84 (s, 2H, regioisomers).

¹H-NMR (5%-pyridine-d₅ in C₆D₆, 75° C., 500 MHz, two regioisomers):1.51, 1.57 and 1.60 (s, 36H regioisomers), 7.08 (t, 2H, J=8 Hz), 7.92(t, 2H, J=9 Hz), 7.99 (d, 4H, J=8 Hz), 8.04 (s, 2H), 8.06 and 8.15 (s,2H, regioisomers), 8.02-8.06 (m, 4H), 8.45 and 8.54 (d, 2H, J=1 Hz,regioisomers), 8.90 and 8.93 (d, 2H, J=4.5 Hz, regioisomers), 9.11 and9.13 (s, 2H, regioisomers), 9.23-9.30 (m, 4H), 9.67 and 9.70 (s, 2H,regioisomers).

¹³C-NMR (5%-pyridine-d₅ in C₆D₆, 25° C., 125 MHz, two regioisomers):30.1, 31.84, 31.92, 31.94, 35.20, 114.0, 114.2, 121.1, 121.3, 121.4,122.7, 124.1, 124.2, 124.8, 125.4, 125.41, 125.8, 126.4, 126.9, 127.4,127.42, 127.5, 128.9, 129.0, 130.3, 130.5, 130.7, 130.8, 131.8, 132.0,132.9, 133.0, 133.03, 133.3, 133.4, 133.6, 136.5, 136.6, 138.0, 138.4,143.3, 143.4, 146.7, 147.4, 149.2, 150.1, 150.4, 150.5, 150.8, 151.1.

UV/VIS (CH₂Cl₂), λ, nm, (ε): 815 (101541), 735 (27675), 651 (9565), 526(141945), 505 (138669).

Emission (CH₂Cl₂): λ_(max), 815 nm; quantum yield, 10%.

MALDI TOF: 1143.9 (M⁺), requires 1144.44 for C₈₀H₆₄N₄Zn. HRMS: 1144.4418(M⁺), calcd. 1144.4417 for C₈₀H₆₄N₄Zn.

Elemental analysis for C₈₀H₆₄N₄Zn*MeOH: calcd.: C, 82.53; H, 5.81; N,4.75. found: C, 82.92; H, 5.77; N, 4.78.

[10,20-Bis(3,5-di-tert-butylphenyl)-5,7,15,17-bis-(1,10-pyrenyl)-porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc)(II) compound anti-ZnDFBPP. anti-ZnDFBPP can beobtained by separation of a mixture of anti/syn ZnDFBPP using silica gelcolumn (gradient elution with benzene:hexanes-1:5 to 2:3) by collectingfirst fraction followed by layered crystallization fromdichloromethane:methanol mixture. R_(f)=0.42 (hexanes:benzene=1:1).

¹H-NMR (5%-pyridine-d₅ in C₆D₆, 25° C., 500 MHz): 1.59 (s, 36H, t-Bu),7.83 (t, 2H, J=8 Hz, H_(pyrene)), 7.93 (d, 2H, J=9 Hz, H_(pyrene)), 7.99(d, 2H, J=9 Hz, H_(pyrene)) 8.00 (d, 2H, J=8 Hz, H_(pyrene)), 8.05 (d,2H, J=8 Hz, H_(pyrene)), 8.04 (t, 2H, J=1.5 Hz, p-H of Ar), 8.27 (d, 2H,J=9, Hz, H_(pyrene)), 8.50-8.51 (m, 2H, o-H of Ar), 8.55 (d, 2H, J=1.5Hz, o-H of Ar), 9.00 (d, 2H, J=4.5 Hz, β-pyrrolic H_(porph)) 9.13 (s,2H, β-pyrrolic H_(porph)) 9.27 (d, 2H, J=4.5 Hz, β-pyrrolic H_(porph)),9.33 (d, 2H, J=8 Hz, H_(pyrene)) 9.84 (s, 2H, H_(pyrene).

¹³C-NMR (5%-pyridine-d₅ in C₆D₆, 125 MHz): 32.0, 35.3, 114.3, 121.3,122.9, 124.4, 124.5, 125.4, 125.9, 126.4, 126.75, 126.81, 127.4, 129.2,130.5, 130.8, 131.8, 132.0, 133.0, 133.3, 133.5, 136.7, 138.1, 143.4,146.8, 149.5, 150.2, 150.4, 151.2.

UV/VIS (CH₂Cl₂), λ, nm, (ε): 815 (81206), 741 (20628), 656 (5045), 559(54452), 504 (151197). Emission (CH₂Cl₂): λ_(max), 839 nm; quantumyield, 7.7%.

[10,20-Bis(3,5-di-tert-butylphenyl)-3,5,15,17-bis-(1,10-pyrenyl)-porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) compound syn-ZnDFBPP. syn-ZnDFBPP can beobtained by separation of a mixture of anti/syn ZnDFBPP using silica gelcolumn (gradient elution with benzene:hexanes-1:5 to 2:3) by collectingthe last fractions followed by layered crystallization fromdichloromethane-methanol mixture. R_(f)=0.31 (hexanes:benzene=1:1).

¹H-NMR (5%-pyridine-d₅ in C₆D₆, 25° C., 500 MHz): 1.53 (s, 18H, t-Bu),1.61 (s, 18H, t-Bu), 7.82 (t, 2H, J=8 Hz, H_(pyrene)), 7.93 (d, 2H, J=9Hz, H_(pyrene)) 7.99 (d, 2H, J=9 Hz, H_(pyrene)), 8.00 (t, 1H, J=1.5 Hz,p-H of Ar), 8.00 (d, 2H, J=8 Hz, H_(pyrene)), 8.05 (d, 2H, J=8 Hz,H_(pyrene)), 8.17 (t, 1H, J=1.5 Hz, p-H of Ar), 8.27 (d, 2H, J=9 Hz,H_(pyrene)), 8.40 (2, 2H, J=1.5 Hz, o-H of Ar), 8.61 (d, 2H, J=1.5 Hz,o-H of Ar), 9.07 (d, 2H, J=4.5 Hz, β-pyrrolic H_(porph)), 9.08 (s, 2H,β-pyrrolic H_(porph)), 9.36 (d, 2H, J=4.5 Hz, β-pyrrolic H_(porph)),9.37 (d, 2H, J=8 Hz, H_(pyrene)), 9.78 (s, 2H, H_(pyrene)).

¹³C-NMR (5%-pyridine-d₅ in C₆D₆, 125 MHz): 30.2, 31.9, 32.0, 114.0,121.1, 121.4, 122.52, 122.54, 123.3, 123.34, 124.3, 125.0, 125.5, 125.9,126.3, 126.8, 127.4, 127.5, 128.6, 128.7, 128.8, 129.0, 129.7, 129.85,129.9, 130.5, 130.80, 130.85, 131.8, 131.9, 132.9, 133.0, 133.7, 136.6,138.5, 143.3, 143.5, 147.4, 149.2, 149.5, 150.6, 150.8.

UV/VIS (CH₂Cl₂), λ, nm, (ε): 811 (91461), 736 (26446), 657 (10865), 527(145812). Emission (CH₂Cl₂): λ_(max), 829 nm; quantum yield, 12.8%.

Example 2 ZnQFTPP

5,15-bis-(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³, κN²⁴)zinc(II). Toa stirred solution of 1-pyrenecarboxaldehyde (3.7 g, 15.92 mmol) and1,1′-dipyrrolomethane (2.34 g, 15.92 mmol) in dichloromethane (2 L)under nitrogen atmosphere trifluoroacetic acid was added (2 ml) and thereaction mixture was stirred at ambient temperature in dark for 24hours. After that DDQ (5.36 g) was added and stirring continued foradditional 1 hour. The reaction mixture was quenched with triethylamine(10 ml) and passed through filter filled with silica gel washing withdichloromethane. All purple fractions were collected, dichloromethaneevaporated and the residue passed through filter filled with aluminawashing with dichloromethane. All purple fractions were collected,dichloromethane was evaporated to volume 500 ml. To this solution of thefree-base bis-pyrenyl-porphyrin 30 ml of saturated solution of zinc(II)acetate was added and the resulting mixture was stirred for 3 hours atambient temperature. The reaction mixture was washed with water anddichloromethane solution was passed through filter filled with silicagel washing with dichloromethane. The residue after evaporation ofsolvent was crystallized from dichloromethane-methanol mixture to give5,15-bis-(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³, κN²⁴)zinc(II)(430 mg, 0.56 mmol, 7%).

10,20-bis-bromo-5,15-bis-(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³,κN²⁴)zinc(II). NBS (194 mg, 1.09 mmol, 2.1 equiv.) was added to astirred solution of the above 5,15-bis-(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (402 mg, 0.519 mmol) in dichloromethane (300ml) and pyridine (5 ml) at −10° C. (NaCl/ice bath) under nitrogenatmosphere. The reaction mixture was stirred at the same temperature for10 minutes the was allowed to warm to 0° C. in a water bath for 5minutes and was quenched with acetone (20 ml). The crude reactionmixture was passed through silica gel column, eluting withdichloromethane-pyridine mixture (100:1). All green-purple fractionswere collected, solvents were evaporated, the residue was dissolved indichloromethane-pyridine mixture (95:5, 100 ml) and 200 ml of methanolwas added to precipitate brominated porphyrin. All crystals werecollected by filtration after 30 min to give10,20-bis-bromo-5,15-bis-(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³,κN²⁴)zinc(II) (435 mg, 0.47 mmol, 90%).

¹H-NMR (5% pyridine-d5 in CDCl₃, 500 MHz): 6.93 (t, 2H, J=8 Hz), 7.19(d, 2H, J=10 Hz), 7.61 (d, 2H, J=10 Hz), 8.06-8.09 (m, 4H), 8.32-8.36(m, 4H), 8.42 (d, 2H, J=8 Hz), 8.52 (d, 4H, J=4.5 Hz), 8.79 (d, 2H, J=8Hz), 9.55 (d, 4H, J=4.5 Hz).

5,10,15,20-tetrakis-(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³,κN²⁴)zinc(II) ZnTPP. A mixture of the above10,20-bis-bromo-5,15-bis-(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³,κN²⁴)zinc(II) (400 mg, 0.429 mmol), cesium carbonate (1.45 g, 10equiv.), Pd(PPh₃)₄ (50 mg, 10 mol %) water (0.5 ml) and 1-pyrenylboronicacid (232 mg, 0.95 mmol, 2.2 equiv.) in toluene (150 ml) and pyridine (2ml) was degassed and reflux in nitrogen atmosphere for 12 hours. Thereaction mixture was cooled and passed consecutively through pad ofcelite, silica gel and neutral alumina washing with toluene. Toluene wasdistilled off in vacuum, the residue was separated by crystallizationfrom dichloromethane-methanol to afford5,10,15,20-tetrakis-(1-pyrenyl)porphyrinato(2-)-κN²¹, κN²², κN²³,κN²⁴)zinc(II) (260 mg, 0.221 mmol, 52%).

¹H-NMR (5% pyridine-d5 in CDCl₃, 500 MHz, mixture of atropoisomers):7.46-7.66 (m, 8H), 7.98-8.07 (m, 8H), 8.13-8.19 (m, 4H), 8.23-8.33 (m,8H), 8.44-8.48 (m, 8H), 8.76-8.87 (m, 4H). MALDI TOF: 1172.6 (M⁺),requires 1172.29 for C₈₄H₄₄N₄Zn.

4,5,9,10,14,15,19,20-tetrakis-(1,10-pyrenyl)porphyrinato(2-)-κN²¹, κN²²,κN²³, κN²⁴)zinc(II) ZnQFTPP. The above tetrakis-pyrenyl-porphyrinZnTPP*MeOH (48 mg, 0.0399 mmol) in a glass tube under nitrogen flow wasplaced into oven preheated to 530° C. The oven temperature rose to 530°C. in 1-2 minutes and after additional approx. 1 minute startingmaterial melted. Heating continued for approx. 2 minutes until reactionmixture turned into dark color and the first bubbles appeared. The tubewas cooled to room temperature under nitrogen. The crude mixture wasdissolved in dichloromethane (500 ml) with addition of pyridine (5 ml)and passed through filter filled with silica gel washing withdichloromethane and then pyridine to wash ZnQFTPP. Yield: 22 mg, 49%.

¹H-NMR (dilute solution in 5%-pyridine-d₅ in C₆D₆, 75° C., 600 MHz,signal assignment for possible regioisomers could not be done, longeracquisition time required, signal broadening due to aggregation): 7.63(d, 4H, J=8 Hz), 7.74-7.84 (m, 12H), 7.88-7.97 (m, 16H), 8.03 (d, 4H,J=9 Hz).

UV/VIS (5% pyridine in CH₂Cl₂), λ, nm (ε): 1003 (13954), 873 (43861),813 (30458), 620 (73072), 576 (70842).

MALDI-TOF MS (without matrix): 1164.32 (M⁺), requires 1164.22 forC₈₄H₃₆N₄Zn. Peak of the molecular ion could not be obtained by usingHRMS (ESI/APCI).

¹³H-NMR (5% pyridine-d₅ in C₆D₆, 125 MHz, weak signals): 124.0, 125.07,125.10, 125.17, 126.10, 126.15, 126.8, 127.4, 127.5, 128.9, 129.6,129.9, 131.6.

Example 3 ZnFBTP

[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis(3-benzothienyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) ZnBTP. A mixture of the above[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis-bromo-porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (3.4 g, 3.74 mmol), cesium carbonate (10 g, 70mmol, 8 equiv.), Pd(PPh₃)₄ (440 mg, 10 mol %) water (3 ml) and3-benzothienylboronic acid (1.67 g, 9.38 mmol, 2.5 equiv.) in toluene(600 ml) and pyridine (6 ml) was degassed and reflux in nitrogenatmosphere for 12 hours. The reaction mixture was cooled and passedconsecutively through pad of celite, silica gel and neutral aluminawashing with toluene. Toluene was distilled off in vacuum, the residuewas separated by crystallization from dichloromethane-methanol to afford[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis(3-benzothienyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) ZnBTP (3.03 g, 2.99 mmol, 80%).

¹H-NMR (CDCl₃, 400 MHz): 1.51 (s, 36H), 3.32 (dd, 2H, J=1, 6 Hz),7.19-7.22 (m, 2H), 7.24 (s, 2H), 7.47 (t, 2H, J=7 Hz), 7.78 (t, 2H,J=1.5 Hz), 8.06-8.11 (m, 4H), 8.19 (d, 2H, J=7 Hz), 8.93 (dd, 4H, J=1,4.5 Hz), 8.96 (dd, 4H, J=1, 4.5 Hz).

¹³C-NMR (CDCl₃, 75 MHz): 31.7, 35.0, 113.3, 120.8, 122.5, 122.6, 124.46,124.54, 124.69, 124.7, 129.2, 129.3, 129.7, 129.8, 129.9, 131.5, 132.6,138.45, 138.50, 141.6, 144.48, 144.49, 148.55, 148.57, 148.59, 150.6,150.7.

UV/VIS (CH₂Cl₂) λ, nm, (ε): 589 (4100), 550 (20886), 423 (498623).

MALDI TOF: 1012.77 (M⁺), requires 1012.36 for C₆₄H₆₀N₄S₂Zn.

[10,20-Bis(3,5-di-tert-butylphenyl)-3,5-bis(2,3-benzothienyl)-15-(3-benzothienyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) ZnFBTP. The above porphyrin ZnBTP (870 mg,0.86 mmol) and anhydrous iron(III) chloride (2.5 g, 15.4 mmol, 18equiv.) were stirred in anhydrous dichloromethane (500 ml) undernitrogen atmosphere at 20° C. (water bath) for 2 hours. The reactionmixture was quenched with pyridine (10 ml), washed with water and passedthrough pad with silica gel eluting with dichloromethane. Solution ofzinc(II) acetate dihydrate (300 mg) in methanol (50 ml) was added to theabove solution and the mixture was stirred for 2 hours at roomtemperature. The reaction mixture was washed with water and the residueafter evaporation of dichloromethane was subjected to columnchromatography on silica gel, eluting with mixture of hexanes and ethylacetate 1000-3 to 1000-10 ratio. Yield 490 mg (0.48 mmol, 56%).[10,20-Bis(3,5-di-tert-butylphenyl)-3,5-bis(2,3-benzothienyl)-15-(3-benzothienyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) ZnFBTP.

¹H-NMR (5% pyridine-d5 in CDCl₃, 400 MHz): 1.48 and 1.51 (s, 36H), 6.94(t, 1H, J=7.5 Hz), 7.10 (s, 1H), 7.18 (t, 1H, J=7.5 Hz), 7.23 (td, 1H,J=1, 7.5 Hz), 7.36 (d, 1H, J=7.5 Hz), 7.42 (t, 1H, J=7.5 Hz), 7.66 (t,1H, J=1.5 Hz), 7.69 (t, 1H, J=1.5 Hz), 7.75 (t, 1H, J=1.5 Hz), 7.77 (t,1H, J=1.5 Hz), 7.80 (t, 1H, J=1.5 Hz), 7.81 (t, 1H, J=1.5 Hz), 7.92 (s,1H), 7.95 (d, 1H, J=4.5 Hz), 8.00 (d, 1H, J=4.5 Hz), 8.07 (d, 1H, J=4.5Hz), 8.08 (d, 1H, J=8 Hz), 8.14 (d, 1H, J=7.5 Hz), 8.23 (d, 1H, J=8 Hz),8.34 (d, 1H, J=4.5 Hz), 8.85 (d, 1H, J=4.5 Hz).

¹³C-NMR (CDCl₃, 75 MHz): 29.7, 31.7, 35.0, 115.7, 118.1, 120.9, 121.1,121.13, 122.5, 122.9, 123.0, 123.4, 124.0, 124.3, 124.5, 124.53, 125.5,128.4, 128.7, 128.8, 128.9, 129.1, 129.3, 129.5, 131.0, 131.3, 132.6,134.1, 135.2, 137.2, 138.8, 139.1, 140.7, 142.8, 143.3, 145.4, 148.0,148.7, 148.8, 149.0, 149.01, 149.6, 150.5, 151.2, 151.4, 153.8, 154.7,167.7.

UV/VIS (CH₂Cl₂), λ, nm, (ε): 795 (1347), 682 (1560), 622 (5572), 570 sh(3800), 535 (14801), 498 (85163), 470 (54970), 405 (83963), 325 (28938).MALDI TOF: 1010.8 (M⁺), requires 1010.34 for C₆₄H₅₈N₄S₂Zn.

Example 4 Cyano-Phenyl Porphyrin Dimer

[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4-cyanophenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II). (A). NBS (484 mg, 2.72 mmol, 1 equiv.) wasadded to a stirred solution of bis-(3,5-di-tert-butyl-phenyl)-porphyrin(2.034 g, 2.72 mmol) in dichloromethane (280 ml) and pyridine (3.3 ml)at −10° C. (NaCl/ice bath) under nitrogen atmosphere. The reactionmixture was stirred at the same temperature for 10 minutes the wasallowed to warm to 0° C. in a water bath for 5 minutes and was quenchedwith acetone (20 ml). The crude reaction mixture was passed throughsilica gel column, eluting with dichloromethane-pyridine mixture(100:1). All green-purple fractions were collected, solvents wereevaporated, the residue was dissolved in dichloromethane-pyridinemixture (95:5, 100 ml) and 200 ml of methanol was added to precipitatebrominated porphyrins. All crystals were collected by filtration after30 minutes to give a mixture of mono and dibrominated porphyrins (2.39g). This mixture was used for the next step without further separation.

(B). A mixture of the above mono and dibromoporphyrins (1.68 g, approx.2.03 mmol), cesium carbonate (4.8 g, 28 mmol), Pd(PPh₃)₄ (250 mg, 0.22mmol) and 4-cyanophenyl-tetramethyldioxaborolane 1.0 g, 4.37 mmol, 2.16equiv.) in toluene (480 ml) was degassed and refluxed in nitrogenatmosphere for 12 hours. The reaction mixture was cooled and passedconsecutively through pad of celite, silica gel and neutral aluminawashing with toluene. Toluene was distilled off in vacuum, the residuewas separated by column chromatography on silica gel eluating withmixture of hexanes and ethyl acetate to afford[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4-cyanophenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (0.74 g, 0.87 mmol, 43%).

¹H-NMR (CDCl₃, 250 MHz): 1.56 (s, 36H), 7.83 (t, 2H, J=1.5 Hz), 8.04 (d,2H, J=8 Hz), 8.11 (d, 4H, J=1.5 Hz), 8.36 (d, 2H, J=8 Hz), 8.85 (d, 2H,J=4.5 Hz), 9.08 (d, 2H, J=4.5 Hz), 9.15 (d, 2H, J=4.5 Hz), 9.43 (d, 2H,J=4.5 Hz), 9.99 (s, 1H).

{μ-[15,15′-Bis(4-cyanophenyl)-10,10′,20,20′-tetrakis(3,5-di-tert-butylphenyl)-5,5′-biporphyrinato(4-)-κN²¹,κN²², κN²³, κN²⁴, κN^(21′), κN^(22′), κN^(23′), κN^(24′)]}dizinc(II).The above[10,20-Bis(3,5-di-tert-butylphenyl)-5-(4-cyanophenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (720 mg, 0.85 mmol), DDQ (962 mg, 4.24 mmol, 5equiv.) and scandium(III) triflate (2.086 mg, 4.24 mmol, 5 equiv.) weredissolved in toluene (500 ml) under nitrogen atmosphere and the mixturewas stirred at room temperature for 1 hour and heated at reflux foradditional 1 hour. After cooling to room temperature the mixture waspassed consecutively through pad with silica gel (2 times) and pad withalumina (elution with dichloromethane-pyridine mixture 100:1). Solventswere evaporated in vacuum, the residue was dissolved indichloromethane-pyridine mixture (30 ml, 100:1). Fraction 1 containedsingly connected porphyrin dimer. Yield 60 mg (0.035 mmol, 8.3%).

¹H-NMR (CDCl₃, 400 MHz): 1.44 (s, 72H), 7.71 (t, 4H, J=1.5 Hz), 8.08 (d,8H, J=1.5 Hz), 8.12 (d, 4H, J=8 Hz), 8.44 (d, 4H, J=4.5 Hz), 8.72 (d,4H, J=4.5 Hz), 8.91 (d, 4H, J=4.5 Hz), 9.06 (d, 4H, J=4.5 Hz).

¹³C-NMR (CDCl₃, 75 MHz): 29.7, 31.7, 35.0, 111.6, 118.7, 119.2, 119.9,120.9, 122.6, 123.7, 129.6, 130.4, 131.1, 132.5, 132.7, 134.0, 134.9,141.4, 148.2, 148.6, 149.0, 150.3, 151.0, 154.9.

Example 5 Pyrene Porphyrin Trimer

[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II). (A). NBS (1.54 g, 8.7 mmol, 1.3 equiv.) wasadded to a stirred solution of bis-(3,5-di-tert-butyl-phenyl) (5 g, 6.7mmol) in dichloromethane (300 ml) and pyridine (5 ml) at −10° C.(NaCl/ice bath) under nitrogen atmosphere. The reaction mixture wasstirred at the same temperature for 10 minutes, then was allowed to warmto 0° C. in a water bath for 5 minutes and was quenched with acetone (20ml). The crude reaction mixture was passed through silica gel column,eluting with dichloromethane-pyridine mixture (100:1). All green-purplefractions were collected, solvents were evaporated, the residue wasdissolved in dichloromethane-pyridine mixture (95:5, 100 ml) and 200 mlof methanol was added to precipitate brominated porphyrins. All crystalswere collected by filtration after 30 min to give a mixture of mono anddibrominated porphyrins (ratio 2.3:1, 4.9 g, approx. 85%). This mixturewas used for the next step without further separation.

(B). A mixture of the above mono and dibromoporphyrins (ratio of mono-to di-bromoporphyrins 2.3:1, 4 g, approx. 4.7 mmol), cesium carbonate(7.8 g, 24 mmol, 5 equiv.), Pd(PPh3)4 (271 mg, 5 mol %) and1-pyrenyl-tetramethyldioxaborolane (2.32 g, 7.1 mmol) in toluene (700ml) was degassed and reflux in nitrogen atmosphere for 12 hours. Thereaction mixture was cooled and passed consecutively through pad ofcelite, silica gel and neutral alumina washing with toluene. Toluene wasdistilled off in vacuum and the residue was separated by fractionalcrystallization from dichloromethane-methanol and column chromatographyon silica gel eluting with mixture of hexanes and ethyl acetate toafford[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) 2.76 g, 2.9 mmol, 62%) and[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-Bis(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (0.81 g, 0.71 mmol, 15%).

[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II). ¹H-NMR (CDCl₃, 400 MHz): 1.54 (s, 36H), 7.43(d, 1H, J=9.3 Hz), 7.67 (d, 1H, J=9.3 Hz), 7.60 (s, 2H), 8.00-8.18 (m,6H), 8.32 (t, 2H, J=7 Hz), 8.40 (d, 1H, J=9.1 Hz), 8.51 (d, 1H, J=7.7Hz), 8.63 (d, 2H, J=4.6 Hz), 8.82 (d, 1H, J=7.7 Hz), 8.95 (d, 2H, J=4.6Hz), 9.18 (d, 2H, J=4.5 Hz), 9.46 (d, 2H, J=4.5 Hz), 10.33 (s, 1H).

MALDI TOF: 950 (M⁺), requires 948.41 for C₆₄H₆₀N₄Zn.

[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)-10-bromoporphyrin.(A). NBS (48 mg, 0.268 mmol, 1 equiv.) was added to a stirred solutionof porphyrin VII (255 mg, 0.268 mmol) in dichloromethane (150 ml) andpyridine (2 ml) at −10° C. (NaCl/ice bath) under nitrogen atmosphere.The reaction mixture was stirred at the same temperature for 10 min thewas allowed to warm to 0° C. in a water bath for 5 minutes and wasquenched with acetone (20 ml). The crude reaction mixture was passedthrough silica gel column, eluting with dichloromethane-pyridine mixture(100:1). All green-purple fractions were collected, solvents wereevaporated, the residue was dissolved in dichloromethane-pyridinemixture (95:5, 100 ml) and 200 ml of methanol was added to precipitatebrominated porphyrin. All crystals were collected by filtration after 30minutes to give 275 mg (quant) of[10,20-Bis(3,5-di-tert-butylphenyl)-5-(1-pyrenyl)-10-bromoporphyrinato(2+κN²¹,κN²², κN²³, κN²⁴)zinc(II): ¹H-NMR (CDCl₃, 400 MHz): 1.48 and 1.49 (2,36H), 7.54 (d, 1H, J=14 Hz), 7.74 (t, 2H, J=1.5 Hz), 7.98-8.03 (m, 6H),8.23-8.28 (m, 2H), 8.34 (d, 1H, J=9 Hz), 8.42 (d, 2H, J=4.5 Hz), 8.45(s, 1H), 8.75 (d, 2H, J=4.5 Hz), 8.76 (2, 1H, J=8 Hz), 8.96 (d, 2H,J=4.5 Hz), 9.72 (d, 2H, J=4.5 Hz).

(B). To a stirring solution of the above bromo-pyrene substitutedporphyrin in 100 ml of dichloromethane concentrated aq. Hydrochloricacid (2 ml) was added and the reaction mixture was vigorously stirredfor 3 minutes. After that reaction mixture was quenched with pyridine (5ml) and the resulting solution was passed through a filter with silicagel eluting with dichloromethane. The residue after evaporation ofsolvents in vacuum is pure free-base porphyrin.

¹H-NMR (CDCl₃, 400 MHz): 1.55 and 1.56 (2, 36H), 7.40 (d, 1H, J=9 Hz),7.63 (d, 1H, J=9 Hz), 7.75 (t, 2H, J=1.5 Hz), 7.97-8.03 (m, 6H),8.22-8.26 (m, 1H), 8.31 (d, 1H, J=9 Hz), 8.40 (d, 2H, J=4.5 Hz), 8.42(d, 1H, J=8 Hz), 8.69-8.71 (m, 3H), 8.92 (d, 2H, J=4.5 Hz), 9.66 (d, 2H,J=4.5 Hz).

[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II). (A). NBS (2.61 g, 14.7 mmol, 2.2 equiv.) wasadded to a stirred solution of porphyrin I (5 g, 6.7 mmol) indichloromethane (500 ml) and pyridine (5 ml) at −10° C. (NaCl/ice bath)under nitrogen atmosphere. The reaction mixture was stirred at the sametemperature for 10 minutes, then was allowed to warm to 0° C. in a waterbath for 5 minutes and was quenched with acetone (20 ml). The crudereaction mixture was passed through silica gel column, eluting withdichloromethane-pyridine mixture (100:1). All green-purple fractionswere collected, solvents were evaporated, the residue was dissolved indichloromethane-pyridine mixture (95:5, 100 ml) and 200 ml of methanolwas added to precipitate dibromoporphyrin. All crystals were collectedby filtration after 30 minutes to give[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis-bromo-porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (4.76 g, 5.23 mmol, 78%).

¹H-NMR (5%-pyridine-d₅ in CDCl₃, 400 MHz): 1.46 (s, 36H), 7.30 (t, 2H,J=1.5 Hz), 7.91 (d, 4H, J=1.5 Hz), 8.83 (d, 4H, J=4.5 Hz), 9.58 (d, 4H,J=4.5 Hz).

(B). A mixture of dibromoporphyrin (1.05 g, 1.15 mmol), pinacoleborane(5 ml) Cl₂Pd(PPh₃)₂ (170 mg, 0.26 mmol) triethylamine (3 ml) andpyridine (3 ml) in toluene (200 ml) was degassed and reflux in nitrogenatmosphere for 1 hour. The reaction mixture was cooled and quenchedcarefully with water (10 ml drop wise). Toluene was distilled off invacuum, the residue was separated by column chromatography on silica geleluting with mixture of hexanes and ethyl acetate to afford[10,20-Bis(3,5-di-tert-butylphenyl)-5,15-bis(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl)porphyrinato(2-)-κN²¹,κN²², κN²³, κN²⁴)zinc(II) (Fraction 3, 0.3 g).

¹H-NMR (CDCl₃, 400 MHz): 1.63 (s, 36H), 1.90 (s, 24H), 7.89 (t, 2H,J=1.5 Hz), 8.17 (d, 4H, J=1.5 Hz), 9.20 (d, 4H, J=4.5 Hz), 9.99 (d, 4H,J=4.5 Hz).

{μ₃-[10,10″-Bis(1-pyrenyl)-5,5′5″,15,15′15″-hexakis(3,5-di-tert-butylphenyl)-tetracyclo-2,2′:8′2″-terporphyrinato(6-)-κN²¹,κN²², κN²³, κN²⁴: κN^(21′), κN^(22′), κN^(23′), κN^(24′): κN^(21″),κN^(22″), κN^(23″), κN^(24″)]}trizinc(II) pyrene porphyrin trimer. (A).A mixture of porphyrin VI (118 mg, 0.118 mmol), porphyrin VIII (250 mg,2.2 equiv.), Pd(PPh₃)₄ (27 mg, 0.26 mmol) and cesium carbonate (197 mg,0.588 mmol) in toluene (20 ml) and DMF (10 ml) was degassed and heatedto 90° C. in nitrogen atmosphere for 20 hours. The reaction mixture wascooled and washed with water (3×100 ml). Toluene was distilled off invacuum and the residue was subjected to GPC column first (BioRadpolystyrene-divinylbenzene copolymer beads, toluene). The first fractionwas collected and subjected to column with silica gel eluting withhexanes-ethyl acetate mixtures. The first fraction was collected and theresidue after evaporation of solvents was crystallized fromdichloromethane-methanol mixture to give 30 mg (0.012 mmol, 10%) of{μ₃-[10,10″-Bis(1-pyrenyl)-5,5′5″,15,15′15″-hexakis(3,5-di-tert-butylphenyl)-tetracyclo-2,2′:8′2″-terporphyrinato(6-)-κN^(21′),κN^(22′), κN^(23′), κN^(24′)]}zinc(II).

¹H-NMR (CDCl₃, 400 MHz): −1.87 (s, 4H), 1.26 (s 36H), 1.38 (t, 18H, J=3Hz), 1.44 (d, 36H, J=3 Hz), 1.54 (s, 36H), 7.61 (d, 2H, J=9 Hz), 7.63(t, 2H, J=1.5 Hz), 7.70 (t, 4H, J=1.5 Hz), 7.79 (d, 2H, J=9 Hz),8.10-8.15 (m, 14H), 8.20 (d, 4H, J=4.5 Hz), 8.30 (t, 4H, J=4.5 Hz),8.35-8.38 (m, 4H), 8.45 (d, 2H, J=9 Hz), 8.58-8.60 (m, 6H), 8.70 (d, 4H,J=4.5 Hz), 8.79 (t, 4H, J=4.5 Hz), 8.84 (d, 4H, J=4.5 Hz), 8.92 (d, 4H,J=4.5 Hz).

¹³C-NMR (CDCl₃, 75 MHz): 29.7, 31.7, 35.0, 105.0, 118.2, 118.9, 119.5,120.9, 121.0, 122.5, 122.8, 124.2, 124.7, 125.3, 125.6, 126.3, 127.4,127.7, 127.8, 128.0, 129.3, 129.6, 129.8, 130.9, 131.5, 131.8, 132.4,132.6, 133.5, 134.0, 137.3, 140.9, 141.5, 148.4, 148.7, 150.6, 153.8,154.8.

UV/VIS (CH₂Cl₂), λ, nm, (ε): 243 (118450), 264 (60690), 275 (76840), 323(58970), 338 (66590), 417 (264100), 475 (234730), 523 (74990), 562(68250), 597 (29200), 705 (2000).

(B). To a solution of the above porphyrin trimer (20 mg) indichloromethane (100 ml) solution of zinc(II) acetate (100 mg) inmethanol (5 ml) was added and reaction mixture was kept at roomtemperature for 12 hours. After that solvents were removed in vacuum,the residue was passed through filter with silica gel eluting withdichloromethane. The final product was crystallized fromdichloromethane-methanol mixture to afford{μ₃-[10,10″-Bis(1-pyrenyl)-5,5′5″,15,15′15″-hexakis(3,5-di-tert-butylphenyl)-tetracyclo-2,2′:8′2″-terporphyrinato(6-)-κN²¹,κN²², κN²³, κN²⁴: κN^(21′), κN^(22′), κN^(23′), κN^(24′): κN^(21″),κN^(22″), κN^(23″), κN^(24″)]}trizinc(II) pyrene porphyrin trimer.

¹H-NMR (CDCl₃, 400 MHz): 1.26 (s, 36H), 1.38 (t, 36H, J=3 Hz), 1.44 and1.45 (s, 36H), 7.58 (d, 2H, J=9 Hz), 7.62 (t, 2H, J=1.5 Hz), 7.70 (t,4H, J=1.5 Hz), 7.78 (d, 2H, J=9 Hz), 8.09-8.16 (m, 14H), 8.25 (d, 2H,J=4.5 Hz), 8.29 (d, 2H, J=4.5 Hz), 8.31 (d, 4H, J=4.5 Hz), 8.35-8.38 (m,4H), 8.46 (d, 2H, J=9 Hz), 8.59 (d, 2H, J=9 Hz), 8.69 (d, 4H, J=4.5 Hz),8.78-8.81 (m, 4H), 8.81 (d, 4H, J=4.5 Hz), 8.94 (d, 2H, J=9 Hz), 8.96(d, 4H, J=4.5 Hz).

¹³C-NMR (CDCl₃, 75 MHz): 28.7, 30.6, 33.9, 118.2, 118.8, 119.2, 119.8,121.7, 122.4, 123.0, 123.2, 123.7, 124.2, 124.4, 125.2, 126.5, 126.7,126.9, 128.4, 128.5, 128.6, 129.8, 130.4, 130.8, 131.0, 131.1, 131.3,131.5, 132.5, 132.9, 136.9, 140.5, 147.4, 147.5, 149.3, 149.5, 149.89,149.93, 153.8, 153.9.

Examples of photovoltaic (PV) devices: PV cells were grown on ITO-coatedglass substrates that were solvent cleaned and treated in UV-ozone for10 minutes immediately prior to loading into high vacuum chamber (basepressure 1-3×10⁻⁶ Torr). The following organic materials were purchasedfrom commercial sources: C₆₀ (MTR Limited),2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (Aldrich) and werepurified by sublimation prior to use. Metal cathode material (Al) wereused as received (Alfa Aesar). Materials were sequentially grown byvacuum thermal evaporation at the following rates: C₆₀ (2 A/sec), BCP (2A/sec), Al (3-5 A/sec). The cathode was evaporated through a shadow maskwith 1 mm diameter openings. For solution processed donor, the layerswere spin coated for 40 sec. at 2000 rpm for a final thickness of 100 Å.Current-voltage (I-V) characteristics of the PV cells were measuredunder simulated AM1.5G solar illumination (Oriel Instruments) using aKeithley 2420 3A Source Meter. Donor layer thicknesses and amount ofadditives were experimentally modified for highest power conversionefficiency.

The foregoing description and examples have been set forth merely toillustrate the invention and are not intended to be limiting. Each ofthe disclosed aspects and embodiments of the present disclosure may beconsidered individually or in combination with other aspects,embodiments, and variations of the invention. In addition, unlessotherwise specified, none of the steps of the methods of the presentdisclosure are confined to any particular order of performance.Modifications of the disclosed embodiments incorporating the spirit andsubstance of the invention may occur to persons skilled in the art andsuch modifications are within the scope of the present invention.

We claim:
 1. A compound comprising a non-activated porphyrin fused withone or more non-activated heterocyclic rings, said compound having aformula selected from the group consisting of:

wherein M is two hydrogen atoms or any element selected from the groupconsisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn,Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al,Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Th, and U; wherein R₁-R₁₄ are independently selectedfrom the group consisting of hydrogen, alkyl, fluoroalkyl, hydroxyl,alkoxy, halo (Cl, Br, I), chalcogens (S, Se, Te), mercapto group, amino,cyano, alkenyl, alkynyl, and aryl; wherein X is O, S, Se, Te, N, P, As,Si, Ge, or B; and each dotted arc is all possible combinations of fusednon-activated rings, both aromatic and unsaturated or combinations ofboth aromatic and unsaturated rings including four, five, six, seven,eight, or nine-membered rings, and all possible combinations of fusedheterocyclic rings with one or more heteroatoms, including all possiblecombinations of all heteroatoms in all possible arrangements.
 2. Thecompound of claim 1, wherein the porphyrin and at least one of theheterocyclic rings are fused in (meso,β) mode.
 3. The compound of claim1, wherein the porphyrin and at least one of the heterocyclic rings arefused in (β,meso, β) mode.
 4. The compound of claim 1, wherein the oneor more non-activated heterocyclic rings are selected from the groupconsisting of:

wherein the wave-line represents the fusion position of the heterocyclicrings to the porphyrin; and wherein the dot represents the point wherethe heterocyclic rings are connected to the meso position of theporphyrin.
 5. A photosensitive device comprising: a first electrode; asecond electrode; and a photoactive region provided between the firstelectrode and the second electrode, wherein the photoactive regioncomprising: a donor material; and an acceptor material, wherein donormaterial is a compound comprising a non-activated porphyrin fused withone or more non-activated heterocyclic rings, said compound having aformula selected from the group consisting of:

wherein M is two hydrogen atoms or any element selected from the groupconsisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Nb, Ta, Cr, Mo, W, Mn,Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al,Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb, Bi, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, Lu, Th, and U; wherein R₁-R₁₄ are independently selectedfrom the group consisting of electron donor and acceptor groups, such ashydrogen, alkyl, fluoroalkyl, hydroxyl, alkoxy, halo (Cl, Br, I),chalcogens (S, Se, Te), mercapto group, amino, cyano, alkenyl, alkynyl,and aryl; wherein X is O, S, Se, Te, N, P, As, Si, Ge, or B; and eachdotted arc is all possible combinations of fused rings, both aromaticand unsaturated or combinations of both aromatic and unsaturated ringsincluding four, five, six, seven, eight, or nine-membered rings, and allpossible combinations of fused heterocyclic rings with one or moreheteroatoms, including all possible combinations of all heteroatoms inall possible arrangements.
 6. The device of claim 5, wherein theporphyrin and at least one of the non-activated heterocyclic rings arefused in (meso,β) mode.
 7. The device of claim 5, wherein the porphyrinand at least one of the non-activated heterocyclic rings are fused in(β,meso, β) mode.
 8. The device of claim 5, wherein the one or morenon-activated heterocyclic rings are selected from the group consistingof:

wherein the wave-line represents the fusion position of the heterocyclicrings to the porphyrin; and wherein the dot represents the point wherethe heterocyclic rings are connected to the meso position of theporphyrin.
 9. A process for fusing one or more non-activated polycyclicrings to a non-activated porphyrin core comprising: heating a quantityof precursor porphyrins to a fusion temperature in an inert gasenvironment, wherein the fusion temperature is associated with theprecursor porphyrins; holding the precursor porphyrins at the fusiontemperature for a predefined period of time until the precursorporphyrins melt and form a mixture of fused porphyrins; cooling themixture of fused porphyrins to room temperature; and separating themixture of fused porphyrins into various fused porphyrin compoundsaccording to claim
 1. 10. The process according to claim 9, wherein thefusion temperature is above melting point of the precursor porphyrins.11. The process according to claim 9, wherein separating the mixture offused porphyrins comprises column chromatography.
 12. The processaccording to claim 9, further comprising purification of the separatedfused porphyrin compounds through recrystallization of the separatedfused porphyrin compounds.
 13. A method for fabricating a photosensitivedevice comprising: depositing a first electrode layer on a substrate;forming a photoactive region over the first electrode, wherein theforming comprises: (a)(1) depositing a layer of organic donor materialover the first electrode and forming an interim structure, wherein theorganic donor material comprising a precursor porphyrin material, (a)(2)thermally fusing the precursor porphyrin material by heating the interimstructure to a fusion temperature in an inert gas environment andholding the interim structure at the fusion temperature for a predefinedperiod of time until the precursor porphyrin material melts and forms alayer of mixture of fused prophyrins, wherein the fusion temperature isassociated with the precursor porphyrin material, and (a)(3) depositinga layer of an organic acceptor material over the layer of organic donormaterial, whereby the organic donor material layer and the organicacceptor material layer form a photoactive region; or (b)(1) depositinga layer of a mixture of an organic donor material and an organicacceptor material over the first electrode and forming an interimstructure, wherein the organic donor material comprises a precursorporphyrin material, and (b)(1) thermally fusing the precursor porphyrinmaterial by heating the interim structure to a fusion temperature in aninert gas environment and holding the interim structure at the fusiontemperature for a predefined period of time until the precursorporphyrin material melts and forms fused porphyrins, wherein the fusiontemperature is associated with the precursor porphyrin material, wherebythe fused porphyrins and the organic acceptor material form the organicphotoactive region; and depositing a second electrode layer over theorganic acceptor material layer.